Chemical Papers

, Volume 72, Issue 11, pp 2893–2898 | Cite as

Bromine formation in solid NaBr/KNO3 mixture and assay of this reaction via bromination of activated aromatics

  • Ida RahuEmail author
  • Ott Kekišev
  • Jaak Järv
  • Peeter Burk
Original Paper


Bromine formation in the mixture of solid NaBr and KNO3 was observed and the process was studied in different acidified organic solvent–water mixtures by monitoring the bromination of acetanilide and other compounds, containing activated aromatic substituents. This assay is based on fast bromination reaction of these aromatic compounds, as differently from the assay of Br2, the brominated aromatics can be easily determined by conventional gas chromatography–mass spectrometry (GC–MS) methods. It was found that bromine was generated autocatalytically on the surface of salt crystals and the reaction was characterized by a lag period, the duration of which depended on reaction conditions, and importantly on the type of the organic solvent in the reaction mixture. As the bromine formation could be easily controlled by reaction conditions, it was suggested that the studied reaction might have practical applications as an environmentally friendly and economically feasible bromination method. It was also shown that the bromination of aromatics followed the mechanism of classical electrophilic aromatic substitution reaction.


Feasible in situ method of bromine formation Reaction with solid salts Eco-friendly reagents Bromination of activated aromatics 



This work was supported by the institutional research funding IUT (IUT20-15) of the Estonian Research Council.

Supplementary material

11696_2018_526_MOESM1_ESM.docx (2.5 mb)
Supplementary material 1 (DOCX 2564 kb)


  1. Atkins PW, Overton TL, Rourke JP, Weller MT, Armstrong FA (2010) The group 15 elements. In: Shriver and Atkins’ inorganic chemistry, 5th edn. Oxford University Press, Oxford, pp 375–397Google Scholar
  2. Bansal RK (1998) Aromatic electrophilic substitution reactions. In: Hyde CW (ed) Synthetic approaches in organic chemistry. Jones & Bartlett Publishers, LondonGoogle Scholar
  3. Choudary BM, Someshwar T, Reddy CV, Kantam ML, Ratnam KJ, Sivaji LV (2003) The first example of bromination of aromatic compounds with unprecedented atom economy using molecular bromine. Appl Catal A Gen 251:397–409. CrossRefGoogle Scholar
  4. Clayden J, Greeves N, Warren S (2012) Radical reactions. In: Organic chemistry, 2nd edn. Oxford University Press, New York, pp 1019–1052Google Scholar
  5. Horváth AK, Nagypál I (2015) Classification of clock reactions. ChemPhysChem 16:588–594. CrossRefPubMedGoogle Scholar
  6. Hou J, Li Z, Jia X-D, Liu Z-Q (2014) Bromination of arenes using I2O5-KBr in water. Synth Commun 44:181–187. CrossRefGoogle Scholar
  7. Kumar L, Mahajan T, Agarwal DD (2012) Bromination of deactivated aromatic compounds with sodium bromide/sodium periodate under mild acidic conditions. Ind Eng Chem Res 51:11593–11597. CrossRefGoogle Scholar
  8. Lengyel I, Nagy I, Bazsa G (1989) Kinetic study of the autocatalytic nitric acid-bromide reaction and its reverse, the nitrous acid-bromine reaction. J Phys Chem 93:2801–2807. CrossRefGoogle Scholar
  9. Maloy JT (1985) Nitrogen. In: Bard AJ, Parsons R, Jordan J (eds) Standard potentials in aqueous solution. Marcel Dekker, New York, pp 127–139Google Scholar
  10. Mendham J, Denney RC, Bassett J, Jeffery GH (1989) Oxidation and reduction processes involving iodine: iodometric titrations. In: Vogel’s textbook of quantitative chemical analysis, 5th edn. Longman Group, Essex, pp 384–400Google Scholar
  11. Nagypál I, Epstein IR (1986) Fluctuations and stirring rate effects in the chlorite–thiosulfate reaction. J Phys Chem 90:6285–6292. CrossRefGoogle Scholar
  12. Narender N, Srinivasu P, Prasad MR, Kulkarni SJ, Raghavan KV (2002) An efficient and regioselective oxybromination of aromatic compounds using potassium bromide and oxone®,*. Synth Commun 32:2313–2318. CrossRefGoogle Scholar
  13. Narender N, Mohan KVVK, Kulkarni SJ, Raghavan KV (2003) Mild and regioselective oxidative bromination of aromatic compounds using ammonium bromide and oxone. J Chem Res 2003:597–598. CrossRefGoogle Scholar
  14. Naresh M, Kumar MA, Reddy MM, Swamy P, Nanubolu JB, Narender N (2013) Fast and efficient bromination of aromatic compounds with ammonium bromide and oxone. Synthesis 45:1497–1504. CrossRefGoogle Scholar
  15. Podgoršek A, Stavber S, Zupan M, Iskra J (2009) Environmentally benign electrophilic and radical bromination ‘on water’: H2O2–HBr system versus N-bromosuccinimide. Tetrahedron 65:4429–4439. CrossRefGoogle Scholar
  16. Reichardt C (2003) Solvent effects on electron-transfer equilibria. In: Solvents and solvent effects in organic chemistry, 3rd edn. Wiley-VCH, Weinheim, pp 137–139Google Scholar
  17. Salakhov MS, Bagmanov BT, Umaeva VS, Bagmanova MI (2008) Oxidative bromination of aniline and its derivatives. Russ J Appl Chem 81:1479–1481. CrossRefGoogle Scholar
  18. Sharma SK, Agarwal DD (2014) NH4Br-Br2 catalysed oxidative bromination of aromatic compounds. J Agric Life Sci 1:65–81Google Scholar
  19. Skoog DA, West DM, Holler FJ, Crouch SR (2013a) Applications of oxidation/reduction titrations. In: Simpson C (ed) Fundamentals of analytical chemistry, 9th edn. Brooks/Cole, Cengage Learning, Belmont, pp 509–534Google Scholar
  20. Skoog DA, West DM, Holler FJ, Crouch SR (2013b) Applications of standard electrode potentials. In: Simpson C (ed) Fundamentals of analytical chemistry, 9th edn. Brooks/Cole, Cengage Learning, Belmont, pp 473–508Google Scholar
  21. Skoog DA, West DM, Holler FJ, Crouch SR (2013c) Chemicals, apparatus, and unit operations of analytical chemistry. In: Simpson C (ed) Fundamentals of analytical chemistry, 9th edn. Brooks/Cole, Cengage Learning, Belmont, pp 15–47Google Scholar
  22. Skoog DA, West DM, Holler FJ, Crouch SR (2013d) Titrations in analytical chemistry. In: Simpson C (ed) Fundamentals of analytical chemistry, 9th edn. Brooks/Cole, Cengage Learning, Belmont, pp 302–321Google Scholar
  23. Szél V, Csekő G, Horváth AK (2014) Kinetics and mechanism of the oxidation of bromide by periodate in aqueous acidic solution. J Phys Chem A 118:10713–10719. CrossRefPubMedGoogle Scholar
  24. Tajik H, Shirini F, Hassan-zadeh P, Rashtabadi HR (2005) Bromination of aromatic compounds with potassium bromide in the presence of poly(4-vinylpyridine)-supported bromate in nonaqueous solution. Synth Commun. CrossRefGoogle Scholar
  25. Valkai L, Csekő G, Horváth AK (2015) Initial inhomogeneity-induced crazy-clock behavior in the iodate–arsenous acid reaction in a buffered medium under stirred batch conditions. Phys Chem Chem Phys 17:22187–22194. CrossRefPubMedGoogle Scholar
  26. Yousefi J, Tajeian K, Kolvari E, Koukabi N, Khazaei A, Zolfigol MA (2012) A green protocol for the bromination and iodination of the aromatic compounds using H5IO6/NaBr and H5IO6/NaI in the water. Bull Korean Chem Soc 33:2619–2622. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2018

Authors and Affiliations

  • Ida Rahu
    • 1
    Email author
  • Ott Kekišev
    • 1
  • Jaak Järv
    • 1
  • Peeter Burk
    • 1
  1. 1.Institute of ChemistryUniversity of TartuTartuEstonia

Personalised recommendations